CN109796982A - A kind of soil remediation stabilizer and its preparation method and application prepared by high iron tailings - Google Patents
A kind of soil remediation stabilizer and its preparation method and application prepared by high iron tailings Download PDFInfo
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Abstract
The present invention is a kind of soil remediation stabilizer and its preparation method and application prepared by high iron tailings.The raw material components of the reparation stabilizer include: high iron tailings, flyash, hydroxyapatite, molybdenite；Mass fraction in each component are as follows: 40 ~ 60 parts of high iron tailings, 10 ~ 30 parts of flyash, 10 ~ 30 parts of hydroxyapatite, 10 ~ 20 parts of molybdenite；By mixing and ball milling in preparation, then hydro-thermal is carried out, finally a kind of soil remediation stabilizer for heavy-metal contaminated soil reparation is made in drying.Preparation method of the present invention is simple, and raw material is easy to get, and Costco Wholesale is low, and use process is simple to operation, and curing time is short, has solidification effect to common soil pollution element Cu, Pb, Cd, Ni, Zn.
Description
Technical field
The present invention relates to the reparations of heavy-metal contaminated soil, and in particular to a kind of high iron tailings preparation soil remediation stabilizer
Methods and applications.
Background technique
In recent years, industrialization and urbanization progress faster, soil pollution are on the rise.Heavy metal pollution is the main of soil
One of type, heavy metal pollution of soil are primarily due to the unreasonable exploitation of mineral resources, and nonstandard smelting is discharged, and soil is long-term
The application of sewage irrigation, the precipitating of dust caused by mankind's activity and chemical fertilizer and pesticide leads to soil pollution.The weight of contaminated soil
Metal includes cadmium (Cd), and mercury (Hg), lead (Pb) and metalloid arsenic (As) etc. have significant bio-toxicity element, and have certain
Toxicity element such as zinc (Zn), copper (Cu), nickel (Ni) etc..Metal pollutant is low in soil mobility, and micro- life will not occur
Object degradation or chemical degradation, lead to soil degradation, and crop and yield decline.In addition, heavy metal can pass through food chain richness
Collection eventually enters into human body, harm health.
Currently, restoration of soil polluted by heavy metal generally has physical method, chemical method, bioanalysis.Physical method and bioanalysis, it is main
Heavy metal to be removed from soil by engineering technology, there are processing cost height, and processing area is small, and processing time length etc. lacks
Point.The advantages that chemical method has processing area big, and processing cost is low, and project amount is small is that current restoration of soil polluted by heavy metal is most normal
Method.Chemical method mainly repairs stabilizer and changes heavy metal state in the soil by adding to soil, reduce its
Soil mobility rate and bioavailability.
Existing majority soil remediation stabilizer can only have repair to single heavy metal, and heavy metal pollution of soil is logical
It is commonly present various heavy, part soil remediation stabiliser materials are at high cost, and promotion is low.Meanwhile part soil remediation
Stabilizer be easy to cause soil secondary pollution.
The Chinese Patent Application No. CN201810722142.7 date of application is that the patent application document of 2018.07.04 discloses
A kind of multifunction soil improver, this method gather desulfurized gypsum, humic acid, loaded by polystyrene polyamidoamine resin
Acrylamide, citric acid, urea part, magnesium sulfate, calcium gluconate, compound amino acid and the adsorption aid made of silica
It is compound, obtain a kind of soil conditioner, various heavy in energy stable soil.But modifying agent preparation process itself is complicated, part
Cost of material is at high cost, and the soil conditioner rehabilitating soil needs sowed three times, use process is cumbersome, project amount compared with
Greatly, curing time is too long.
Summary of the invention
It is stable it is an object of the present invention in view of the problems of the existing technology, provide a kind of high iron tailings preparation soil remediation
The methods and applications of agent.The present invention is raw material using high iron tailings and molybdenite, by appropriate ratio mixing and ball milling, then is carried out
Hydro-thermal, finally a kind of soil remediation stabilizer for heavy-metal contaminated soil reparation is made in drying.Preparation method letter of the present invention
Single, raw material is easy to get, and Costco Wholesale is low, and use process is simple to operation, and curing time is short, to common soil pollution element Cu, Pb,
Cd, Ni, Zn have solidification effect, and using solid waste such as high iron tailings and flyash, realize the money of solid waste
Sourceization utilizes, and achievees the purpose that with pollution treatment of giving up, and will not generate secondary pollution.
The technical solution of the present invention is as follows:
A kind of soil remediation stabilizer prepared by high iron tailings, the raw material components for repairing stabilizer include: high iron tailings,
Flyash, hydroxyapatite, molybdenite；Mass fraction in each component are as follows: 40~60 parts of high iron tailings, flyash 10~30
Part, 10~30 parts of hydroxyapatite, 10~20 parts of molybdenite；
The high iron tailings is iron tailings of the iron content 10~20%, copper tailing, one of vanadium titanium tailing
Or it is a variety of；The molybdenite contains the MoS that mass percent is 90~95%2。
The preparation method by high iron tailings preparation soil remediation stabilizer.The following steps are included:
(1) by high iron tailings, hydroxyapatite, flyash, molybdenite grinds 1-3h respectively, then crosses 100~200 mesh
Sieve；
(2) by the high iron tailings after grinding, flyash, molybdenite mixes in proportion, submerges 1~2h with strong base solution, so
After take out solid, 500 DEG C~800 DEG C, sintering time is 3~5h；
(3) sintered product is ground, crosses 100~200 meshes；
(4) sintered product after sieving is mixed with the hydroxyapatite after sieving again, and carries out ball milling 1-2h, ball milling produces
Object crosses 100~200 meshes, is then put into water heating kettle afterwards and carries out hydro-thermal reaction, and hydrothermal temperature is 100~250 DEG C, the hydro-thermal time 6
~8h；
(5) it after washing hydrothermal product, in 80~120 DEG C of dry 5~8h, is ground after dry, crosses 100~200 meshes, obtain
To soil remediation stabilizer.
Strong base solution described in step (2) is preferably the sodium hydroxide solution or hydroxide that mass concentration is 30~50%
Potassium solution.
The additive amount of strong base solution described in step (2) is that 0.5~1.5kg powder is added in every liter of strong base solution.
The application method by high iron tailings preparation soil remediation stabilizer, comprising the following steps:
Renovation agent is splashed to contaminated land surface, then is mixed, the soil after maintenance, after being repaired；
Wherein, the additive amount of soil-repairing agent is 500~1000kg/ mus, and hybrid mode is to turn over plough mixing, turns over plough depth and is
30~60cm, curing time are 3-7 days.
Beneficial effects of the present invention:
(1) present invention uses high iron tailings, and the solid waste such as flyash are that primary raw material prepares a kind of soil remediation
Stabilizer realizes the resource utilization of solid waste, achievees the purpose that with pollution treatment of giving up.
(2) preparation process of the present invention is simple to operation, and raw material is cheap and easily-available.Soil remediation fixative economy obtained is real
Favour is known as fixed effect to a variety of soil pollution members, can be substantially reduced Cu in soil, Pb, Cd, the leaching of Ni, Zn using simple
Concentration, repairing effect is good, and curing time is short, and carries out in-situ treatment to contaminated soil, and application method is simple, not will cause secondary
Pollution, as a kind of safety, efficiently, should be worth using with good popularization.In the preferred embodiment, to the coefficient of stabilization of Cu
Reach 98%, 99% is reached to the coefficient of stabilization of Ni, 98% is reached to the coefficient of stabilization of Zn, 99% is reached to the coefficient of stabilization of Pb, to Cd
Coefficient of stabilization reach 99%.The present invention and Chinese Patent Application No. CN201810679715.2, date of application 2018.06.27
Patent application document disclosed in method compare, the present invention to heavy metal have better fixed effect, cost of material is less expensive,
Preparation process is simpler.The present invention and Chinese Patent Application No. CN201810722142.7, date of application are 2018.07.04's
Method disclosed in patent application document is compared, and application method of the invention is simpler, and soil curing time is shorter.
Specific embodiment
Illustrate implementation method of the invention below by way of specific specific example
The present invention provides a kind of preparation method by high iron tailings preparation soil remediation stabilizer.The following steps are included:
S101: by high iron tailings, hydroxyapatite, flyash, molybdenite grinds 1-3h respectively, and grinding product crosses 100~
200 meshes.Wherein high iron tailings be iron content 10%~20% iron tailings, copper tailing, one of vanadium titanium tailing or
It is a variety of.Molybdenite main component is MoS2, purity is 90~95%.
S102: by 40~60 mass parts of high iron tailings of grinding, the mixing of 10~30 mass parts of flyash and molybdenite quality
10~20 parts of part is sufficiently mixed, and submerges 1~2h with strong base solution, is then sintered.Wherein strong base solution is that mass concentration is
40% potassium hydroxide or sodium hydroxide solution, 500~800 DEG C of sintering temperature, 3~5h of sintering time.
S103: sintered product is ground, and crosses 100~200 meshes；
S104: the sintered product after sieving is mixed with 10~30 mass parts of hydroxyapatite after sieving and carries out ball
Mill, Ball-milling Time 1-2h, ball milling product cross 100~200 meshes, are then placed in water heating kettle and carry out hydro-thermal.Wherein hydrothermal temperature is
100 DEG C~250 DEG C, 6~8h. of hydro-thermal time
S105: being dried after hydrothermal product is repeatedly washed, and grinds after dry, crosses 100~200 meshes.Obtain soil
Stabilizer is repaired, wherein 80~120 DEG C of drying temperature, 5~8h. of drying time
The present invention provides a kind of application method of soil remediation fixative.The following steps are included:
S201: toxicity leaching is carried out to soil using HJ/T299-2007, detects soil extract according to HJ781-2016
Middle Cu, Pb, Cd, Ni, the leaching concentration of Zn
S202: renovation agent is uniformly splashed to contaminated land surface, then is uniformly mixed, after maintenance, is repaired
Soil after multiple.Wherein the additive amount of soil-repairing agent is 500~1000kg/ mus, and hybrid mode is to turn over plough mixing, turns over plough depth
For 30~60cm, curing time is 3-7 days.
S203: the step of repeating S201 detects Cu, Pb, Cd in the soil after repairing, Ni, Zn leaching concentration.
It is illustrated combined with specific embodiments below
Embodiment 1
The chemical pollution place that contaminated soil is left after the resettlement of Tianjin pesticide field factory.Using step S201 to its into
Row detection, Main Heavy Metal Cd, Zn, Cu.High iron tailings is iron tailings, comes from Hebei province Luanping County, main component
1.1 are shown in Table, used molybdenite main component MoS2, purity 90%.
Table 1.1: the main component of high iron tailings in embodiment 1
| Quan Tie | Silica | Magnesia | Calcium oxide |
| 10.55% | 41.88% | 14.448% | 13.362% |
(1) preparation of soil-repairing agent stabilizer:
S101: by high iron tailings, hydroxyapatite, flyash, molybdenite grinds 1h respectively, and grinding product sieves with 100 mesh sieve.
S102: by 40 mass parts of high iron tailings of grinding, 20 mass parts of flyash, 20 mass parts of molybdenite mixing, with strong
Aqueous slkali submerges 1h, at 700 DEG C, sintering time 3h.It is 40% sodium hydroxide solution that wherein strong base solution, which chooses mass concentration,
Sodium hydroxide solution (volume mass ratio, L/kg) is added according to the ratio of sodium hydroxide solution and mixture 1:1
S103: sintered product is ground into 1h, is sieved with 100 mesh sieve；
S104: mixing and carry out 1h ball milling with 20 mass parts of hydroxyapatite after sieving for the sintered product after sieving,
Ball milling product crosses 200 meshes, after ball milling, is put into water heating kettle and carries out hydro-thermal.At 250 DEG C, hydro-thermal time 6h.
S105: being dried after hydrothermal product is repeatedly washed, and dry 5h, grinds after dry at 100 DEG C, crosses 200 mesh
Sieve, obtains soil remediation stabilizer.
(2) present invention provides a kind of application method of soil remediation fixative.The following steps are included:
S201: toxicity leaching is carried out to soil using HJ/T299-2007, detects soil extract according to HJ781-2016
Middle Cd, Zn, the leaching concentration of Cu, data are shown in Table 1.2
S202: 500kg/ mus of the additive amount of soil remediation fixative uniformly splashes soil remediation fixative to Polluted Soil
Earth surface, then carry out turning over plough mixing, turning over plough depth is 30cm, is repaired.Curing time 5 days.
S203: the step of repeating S201 detects Cu in the soil after repairing, Cd, Zn leaching concentration.It the results are shown in Table 1.2
Table 1.2: the reparation situation of 1 contaminated soil of embodiment
Embodiment 2
The soil for the Hazardous Wastes Management that contaminated soil is generated from Tianjin metal surface processing factory.Use step S201
It is detected, Main Heavy Metal Cd, Zn, Cu, Pb.High iron tailings is copper tailing, comes from Hebei province Luanping County,
Main component is shown in Table 2.1, used molybdenite main component MoS2, purity 95%.
Table 2.1: in embodiment 2, high tailing main component
| Quan Tie | Silica | Magnesia | Calcium oxide |
| 17.15% | 52.80% | 4.259% | 1.154% |
(1) preparation of soil-repairing agent stabilizer:
S101: by high iron tailings, hydroxyapatite, flyash, molybdenite grinds 2h respectively, and grinding product crosses 200 meshes.
S102: by 40 mass parts of high iron tailings of grinding, 10 mass parts of flyash, 20 mass parts of molybdenite mixing, with strong
Aqueous slkali submerges 2h, at 700 DEG C, sintering time 3h.It is 40% sodium hydroxide solution that wherein strong base solution, which chooses mass concentration,
Sodium hydroxide solution (volume mass ratio, L/kg) is added according to the ratio of sodium hydroxide solution and mixture 1:1
S103: sintered product is ground, and crosses 200 meshes；
S104: the sintered product after sieving is mixed with 30 mass parts of hydroxyapatite after sieving and carries out ball milling, ball
Consume time 1h, and ball milling product crosses 200 meshes, is put into water heating kettle and carries out hydro-thermal.At 250 DEG C, hydro-thermal time 6h.
S105: being dried after hydrothermal product is repeatedly washed, and dry 5h, grinds after dry at 100 DEG C, crosses 200 mesh
Sieve, obtains soil remediation stabilizer.
(2) present invention provides a kind of application method of soil remediation fixative.The following steps are included:
S201: toxicity leaching is carried out to soil using HJ/T299-2007, detects soil extract according to HJ781-2016
Middle Cd, Zn, the leaching concentration of Cu, Pb；Data are shown in Table 2.2
S202: the additive amount of soil remediation fixative is 700kg/ mus, and soil remediation fixative is uniformly splashed to pollution
Soil surface, then carry out turning over plough mixing, turning over plough depth is 40cm, is repaired.Curing time 7 days.
S203: the step of repeating S201 detects Cd, Zn, Cu in the soil after repairing, Pb leaching concentration.It the results are shown in Table 2.2
Table 2.2: the reparation situation of 2 contaminated soil of embodiment
Embodiment 3
Contaminated soil is Tianjin auto parts processing factory contaminated soil.It is detected using step S201, it is main
Wanting heavy metal contaminants is Zn, Cu, and Pb, Ni. high iron tailings are vanadium titanium tailing, comes from Hebei province Luanping County, main component is shown in Table
3.1, used molybdenite main component MoS2, purity 95%.
Table 3.1: the main component of high iron tailings in embodiment 3
| Quan Tie | Silica | Magnesia | Calcium oxide |
| 14.55% | 40.88% | 12.448% | 19.362% |
(1) preparation of soil-repairing agent stabilizer:
S101: by high iron tailings, hydroxyapatite, flyash, molybdenite grinds 2h respectively, and grinding product sieves with 100 mesh sieve.
S102: by 60 mass parts of high iron tailings of grinding, 10 mass parts of flyash, 20 mass parts of molybdenite mixing, with strong
Aqueous slkali submerges 2h, at 800 DEG C, sintering time 4h.It is 40% sodium hydroxide solution that wherein strong base solution, which chooses mass concentration,
Sodium hydroxide solution (volume mass ratio, L/kg) is added according to the ratio of sodium hydroxide solution and mixture 2:1
S103: sintered product is ground, and crosses 200 meshes；
S104: the sintered product after sieving is mixed with 10 mass parts of hydroxyapatite after sieving and carries out ball milling, ball
Consume time 1.5h, and ball milling product crosses 200 meshes, is then placed in water heating kettle and carries out hydro-thermal.At 150 DEG C, hydro-thermal time 5h.
S105: being dried after hydrothermal product is repeatedly washed, and dry 3h, grinds after dry at 100 DEG C, crosses 200 mesh
Sieve, obtains soil remediation stabilizer.
(2) present invention provides a kind of application method of soil remediation fixative.The following steps are included:
S201: toxicity leaching is carried out to soil using HJ/T299-2007, detects soil extract according to HJ781-2016
Middle Ni, Zn, the leaching concentration of Cu, Pb；Data are shown in Table 3.2
S202: the additive amount of soil remediation fixative is 100kg/ mus, and soil remediation fixative is uniformly splashed to pollution
Soil surface, then carry out turning over plough mixing, turning over plough depth is 60cm, is repaired.Curing time 7 days.
S203: the step of repeating S201 detects Ni, Zn, Cu in the soil after repairing, Pb leaching concentration.It the results are shown in Table 3.2
Table 3.2: the reparation situation of 3 contaminated soil of embodiment
Embodiment 4
Contaminated soil moves the soil left by Tianjin electronic component processing factory.It is examined using step S201
It surveys, Main Heavy Metal Zn, Cu, Pb, Ni, Cd.Used high iron tailings is iron tailings and implementation in embodiment 1
The mixing tailing of copper tailing in example 2, ingredient are shown in Table 1.1 and table 2.1, used molybdenite main component MoS2, purity is
95%.
(1) preparation of soil-repairing agent stabilizer:
S101: by high iron tailings, hydroxyapatite, flyash, molybdenite grinds respectively, and hydroxyapatite crosses 200 meshes.
S102: by 40 mass parts of high iron tailings of grinding, 10 mass parts of flyash, 30 mass parts of molybdenite mixing, with strong
Aqueous slkali submerges 2h, at 800 DEG C, sintering time 4h.It is 40% sodium hydroxide solution that wherein strong base solution, which chooses mass concentration,
Sodium hydroxide solution (volume mass ratio, L/kg) is added according to the ratio of sodium hydroxide solution and mixture 2:1
S103: sintered product is ground, and crosses 200 meshes；
S104: the sintered product after sieving is mixed with 20 mass parts of hydroxyapatite after sieving and carries out ball milling, ball
Consume time 1.5h, and ball milling product crosses 200 meshes, is put into water heating kettle and carries out hydro-thermal.At 250 DEG C, hydro-thermal time 3h.
S105: being dried after hydrothermal product is repeatedly washed, and dry 3h, grinds after dry at 120 DEG C, crosses 200 mesh
Sieve, obtains soil remediation stabilizer.
(2) present invention provides a kind of application method of soil remediation fixative.The following steps are included:
S201: toxicity leaching is carried out to soil using HJ/T299-2007, detects soil extract according to HJ781-2016
Middle Ni, Zn, Cu, Pb, the leaching concentration of Cd；Data are shown in Table 4.2
S202: the additive amount of soil remediation fixative is 1000kg/ mus, and soil remediation fixative is uniformly splashed to pollution
Soil surface, then carry out turning over plough mixing, turning over plough depth is 60cm, is repaired.Curing time 7 days.
S203: the step of repeating S201 detects Cd, Zn, Cu in the soil after repairing, Pb, Ni leaching concentration.It the results are shown in Table
4.2
Table 4.2: the reparation situation of 4 contaminated soil of embodiment
Claims (6)
1. a kind of soil remediation stabilizer prepared by high iron tailings, it is characterized in that the raw material components of the reparation stabilizer include:
High iron tailings, flyash, hydroxyapatite, molybdenite；Mass fraction in each component are as follows: 40 ~ 60 parts of high iron tailings, flyash
10 ~ 30 parts, 10 ~ 30 parts of hydroxyapatite, 10 ~ 20 parts of molybdenite；
The high iron tailings is iron tailings of the iron content 10 ~ 20%, copper tailing, one of vanadium titanium tailing or a variety of.
2. the soil remediation stabilizer that the color as belonging to claim 1 is prepared by high iron tailings, it is characterized in that the molybdenite contains
Having mass percent is 90 ~ 95% MoS2。
3. the preparation method of the soil remediation stabilizer prepared as described in claim 1 by high iron tailings, it is characterized in that the party
Method the following steps are included:
(1) by high iron tailings, hydroxyapatite, flyash, molybdenite grinds 1-3h respectively, then crosses 100 ~ 200 meshes；
(2) by the high iron tailings after grinding, flyash, molybdenite mixes in proportion, submerges 1 ~ 2h with strong base solution, then takes out
Solid, 500 DEG C ~ 800 DEG C, sintering time is 3 ~ 5h；
(3) sintered product is ground, crosses 100 ~ 200 meshes；
(4) sintered product after sieving is mixed with the hydroxyapatite after sieving again, and carries out ball milling 1-2h, ball milling product mistake
Then 100 ~ 200 meshes are put into water heating kettle afterwards and carry out hydro-thermal reaction, hydrothermal temperature is 100 ~ 250 DEG C, 6 ~ 8h of hydro-thermal time；
(5) it after washing hydrothermal product, in 80 ~ 120 DEG C of dry 5 ~ 8h, is ground after dry, crosses 100 ~ 200 meshes, obtain soil
Repair stabilizer.
4. the preparation method of the soil remediation stabilizer prepared as claimed in claim 3 by high iron tailings, it is characterized in that the step
Suddenly strong base solution described in (2) is preferably the sodium hydroxide solution or potassium hydroxide solution that mass concentration is 30 ~ 50%.
5. the preparation method of the soil remediation stabilizer prepared as claimed in claim 3 by high iron tailings, it is characterized in that the step
Suddenly the additive amount of strong base solution described in (2) is that 0.5 ~ 1.5kg powder is added in every liter of strong base solution.
6. the application method of the soil remediation stabilizer prepared as described in claim 1 by high iron tailings, it is characterized in that including
Following steps:
Renovation agent is splashed to contaminated land surface, then is mixed, the soil after maintenance, after being repaired；
Wherein, the additive amount of soil-repairing agent is 500 ~ 1000kg/ mu, and hybrid mode is to turn over plough mixing, turn over plough depth for 30 ~
60cm, curing time are 3-7 days.
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| CN114381270A (en) * | 2022-01-27 | 2022-04-22 | 清华大学 | Preparation method of soil remediation agent based on industrial solid waste preparation, soil remediation agent and application thereof |
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